CN104109256A - Preparation method of thiolated chitosan modified polyurethane foam plastic - Google Patents
Preparation method of thiolated chitosan modified polyurethane foam plastic Download PDFInfo
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- CN104109256A CN104109256A CN201410275724.7A CN201410275724A CN104109256A CN 104109256 A CN104109256 A CN 104109256A CN 201410275724 A CN201410275724 A CN 201410275724A CN 104109256 A CN104109256 A CN 104109256A
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Abstract
Thioglycollic acid and chitosan are subjected to an amidation reaction to obtain thiolated chitosan, then the thiolated chitosan is grafted to polyurethane foam plastic by a crosslinking agent glutaraldehyde, and the modified foam plastic can be used to enrich precious metal silver ions. The thiol-modified polyurethane foam plastic has a stronger adsorption ability than that of unmodified polyurethane foam plastic. The saturated adsorption amount of the thiol-modified polyurethane foam plastic can reach 104.8 mg/g according to the linear-regression analysis of the Langmuir adsorption isotherm. The technology is simple, and the thiol-modified polyurethane foam plastic can be used to enrich or recycle precious metal silver ions from industrial sewage or environmental samples.
Description
Technical field
The present invention relates to field of functional materials, relate to a kind of preparation method of Chitosan-Thiolated Polymers modified rigid polyurethane foam, particularly relate to a kind of preparation method's of Chitosan-Thiolated Polymers modified rigid polyurethane foam of enriching noble metals preparation method.
Background technology
Along with scientific and technological progress and development, people produce and life in for precious metal, as the platinum metals of platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), iridium (Ir), osmium (Os) composition and gold (Au) and silver (Ag), demand is increasing.For as electroplating wastewater, mirror waste water processed, gold mine waste, smelting wastewater, film-making workshop waste water, wash in picture waste water and film studio's waste water, contain precious metal, especially gold and silver, need to recycle them.Process for extracting has much in the market, has chemical process, physical method etc.These methods are both advantageous and disadvantageous, and it is poor that different experiment conditions and method have the effect separating.In addition, because precious metal source is abundant, and from different local precious metal samples, there are again diverse ways requirement and the requirement of separation and concentration efficiency.
It is in widespread attention with the analysis of material that separates measured matter that urethane foam can be used as a kind of adsorption and enrichment.In order to widen separation, the enrichment scope of porous plastics, improve the selectivity of its absorption, people carry out modification to porous plastics, by extraction agent, sequestrant and developer even load or be combined in and made loading type porous plastics on porous plastics.Like this, both overcome loading capacity little, the shortcoming of poor selectivity, can improve again the sensitivity of analysis, reduces detection limit.Ren Ying etc. (appoint English, Lei Zhongli, Zhang Jingyu. the research of the dynamic fast separating concentration of porous plastics gold method. analytical chemistry, 1993,21(1): the method for 99～101) having studied the dynamic fast separating concentration gold of porous plastics.And carried out Choice tests to processing the method for foam plastic column, and first boiling porous plastics 10min with deionized water, then boil 10min with 10% hydrochloric acid, and be washed till neutrality with deionized water, earth Using Adsorption of Polyurethane Foam after treatment is respond well in this way.(the Yan Junfeng such as Yan Junfeng, Chen Mingde, Wang Jisen. the research of Chelate foaming plastics separation and concentration precious metal. physical and chemical inspection-chemical fascicle, 1999,35(5): 211～213) application chelating technique has been synthesized the novel C PF-V type porous plastics that contains diphenyl thiourea chelation group, and the condition of CPF-V porous plastics SEPARATION ENRICHMENT OF GOLD WITH and palladium is studied, the preparation of this Chelate foaming plastics is taking resin, isocyanic ester and diphenyl thiourea as raw material, forms the perforate flexible foam containing diphenyl thiourea chelation group through polycondensation, foaming with after solidifying.Because CPF-V porous plastics is to be formed by high polymers parent and analytical functional group diphenyl thiourea chelate group bonding, high stability and highly selective are therefore shown, CPF-V and Au
3+and Pd
2+can form stable inner complex salt and by earth Using Adsorption of Polyurethane Foam.Yang Zhong equality (Yang Zhongping, Jin Xiaozhu, yellow Hua Luan, Wei Shantao .TNA load polyurethane foam plactics enrichment ICP-MS measures Determination of trace gold, platinum, palladium in geochemical sample. assay laboratory, 2006,25(9): 99～102) the strong tri-n-octyl amine of extraction precious metal ability is loaded on urethane foam, drafted tri-n-octyl amine (TNA) load porous plastics fractionation by adsorption ICP-MS method for measuring easy and simple to handle, quick, coefficient of concentration is high.
Generally speaking, exploratory development for urethane foam enriching noble metals is mainly carried out from following two aspects: 1. manage pre-treatment to porous plastics and the absorption of porous plastics and the process of freeing and improve, to reach the object of porous plastics selective adsorption.2. by improving porous plastics and selective reagents, by some extraction agents, sequestrant and developer even load to porous plastics, to form Chelate foaming plastics, ion-exchange porous plastics and the porous plastics etc. that adds lustre to of high adsorption rate and highly selective, thereby widen the range of application of porous plastics separation and concentration.But see on the whole, for the selectivity that how further to improve earth Using Adsorption of Polyurethane Foam; How to improve adsorption rate, the loss while reducing wash-out is to improve the rate of recovery; How to know which kind of material loads on porous plastics, to become which kind of ion or organic sorbent material, especially how reduce costs apply it to curb environmental pollution medium, all need the discussion of system, comprehensive and practice, to further improve the use value of porous plastics in scientific research and production practice.
Sulfydryl, as soft base, is good electron donor, and has stronger complexing action as the precious metal ion of soft acid, is incorporated on resin, chitosan, can obtain the sorbent material that a class is new.The rich bright people's (Ping XiaoFei that waits of river and mountain, Me Enyun. for separating of the resin Recent Advances of, enriching noble metals. ion-exchange and absorption, 1992,8(6): 532～537) synthesized thiol resin RGS-TGA and the RGA-TSH taking poly epihydric alcohol base methylacrylic acid as skeleton: these two kinds of resins have strong anti-atmospheric oxygen voltinism, to Au(
) and Ag(
) there is good adsorption effect, the sulfydryl ammonia type resin taking polystyrene as skeleton is to Au(
) adsorptive power also very strong.Hu Huiling etc. (Hu Huiling, Su Mingang, Xu Jiangping. the preparation of modified chitosan and to Cu
2+, Pb
2+absorption research. ion-exchange and absorption, 2007,23 (3): 274～281) chitosan is carried out to modification, selected the condition of sulfhydrylation.Experiment shows, in the copper solutions that is 188mg/L in concentration, the maximum adsorption rate of CTS-SH reaches more than 90.3%, loading capacity is 27.76mg/g, in the lead solution that is 203mg/L in concentration, plumbous maximum adsorption rate is reached more than 99%, and in the lead solution that is 1.015g/L in concentration, maximum adsorption rate reaches 95.5%.Loading capacity is now 97.4 mg/g, and adsorption rate when loading capacity is greater than 147.2mg/g is 36.3%.Zhang Min etc. (Zhang Min, evergreen, Wang Jinxi, Wang Juan. macromolecule heavy metal flocculant MAC is except Cu
2+go turbid performance. ACTA Scientiae Circumstantiae 2007,27(12): 1994～1999) taking chitosan, Thiovanic acid etc. as raw material has synthesized a kind of novel high polymer heavy metal flocculation agent sulfydryl acetyl chitosan (MAC), studied its copper removal with go turbid mechanism.When MAC and H PAM are when composite, effect is better than using separately MAC, Cu
2+clearance can reach more than 98%.Process Cu with MAC
2+coexist with turbidity system time, the heavy metal ion in waste water and cause absurd creature matter and can play the effect of mutually promoting and removing.
Urethane foam is having greatly utility value as on concentration of precious metal, but therefore current domestic price comparison costliness develops inexpensive and effective polyurethane foam carrier imperative.Chitosan raw material is easy to get, and cost is more cheap than other parents, and good separating effect.But chitosan derivatives class sorbent material is powder conventionally, the later stage separates separating process complexity, consumes energy high.
Summary of the invention
the technical problem solving: inferior separating effect, enrichment narrow range when conventional porous plastics is used for adsorbing precious metal, absorption selectivity low, adsorption rate is low, the object of the present invention is to provide a kind of preparation method of Chitosan-Thiolated Polymers modified rigid polyurethane foam of enriching noble metals, for solving the problems of the prior art.
technical scheme:the present invention adopts waste and old urethane foam as concentration of precious metal carrier, by Chitosan-Thiolated Polymers modified support material, the sulfydryl, the special efficacy sequestering action of amino active group to precious metal that utilize chitosan derivatives to have, obtain the cost-efficiently polyurethane-base functional materials for enriching noble metals.
For achieving the above object and other relevant objects, the invention provides a kind of preparation method of Chitosan-Thiolated Polymers modified rigid polyurethane foam of enriching noble metals, comprise the steps:
(1) in reaction flask, add respectively Thiovanic acid 16ml, diacetyl oxide 8ml, vibration limit, limit drip 4 vitriol oils, fully vibrate cooling after, add chitosan 2g, under stirring, make it under room temperature, react 1h, then in dark place place spend the night;
(2) preparation 200mL, 2mol/LNaOH solution, joins in above-mentioned reaction solution, putting into 70 DEG C of baking ovens leaves standstill after 12h, original resolution of precipitate in solution, then stirs lower adjusting and adds NaOH, measures the pH value of solution, regulate pH value, occur jelly shape red-purple material, suction filtration, embathes except alkali until filtrate is neutral repeatedly with distilled water, filter cake is vacuum-drying 12h at 50 DEG C, and the Chitosan-Thiolated Polymers making is placed in brown bottle and keeps in Dark Place;
(3) Chitosan-Thiolated Polymers making of getting 1 ~ 2g is dissolved in 100mL 2wt% acetum, gets 15 ~ 25cm
3urethane foam immerses in 50mL Chitosan-Thiolated Polymers solution, vacuumize, make to be full of in porous plastics solution, then pipette and be immersed in 50mL, in the glutaraldehyde solution of 0.25wt%, at room temperature react after 4h, repeatedly embathe and make foam be neutral with distilled water, be placed in baking oven dried overnight at 75 DEG C.
Preferably, in described step (2), under stirring, add 1 ~ 10mgNaOH, regulating reacting liquid pH value is 9 ~ 10.
Preferably, in described step (3), get the Chitosan-Thiolated Polymers 1.0g that makes or 1.5g or 2.0g and be dissolved in 100mL 2wt% acetum.
Preferably, in described step (3), preferably get 18 10mm × 10mm × 10mm small cubes urethane foams.
Along with developing rapidly of polyurethane industrial, a large amount of urethane foams need recycling, improve added value of product.Thiovanic acid is organic compounds containing sulfur, according to the hsab theory of Person definition, it belongs to soft base, and the each metal ion species that can and belong to soft acid forms stable inner complex, is also often used as the sequestering agent of the metal ions such as copper, silver, zinc in alkaline medium.Sulfydryl has good keying action to precious metal, so have significant advantage taking chitosan and Thiovanic acid as raw material synthesis modification chitosan for enriching noble metals.The present invention not only utilizes specific surface that urethane foam is large, easily the characteristic such as absorption is improved the stability of chitosan absorbent, and utilize containing dual structure feature and the selectivity of sulfydryl and amino chitosan and improve the adsorptive power to precious metal ion, the chitin modified polyurethane-base functional materials of sulfur-bearing of exploitation can be used for adsorbing the precious metal ion in the environmental samples such as trade effluent, can also be used for gathering and measuring precious metal.
beneficial effect:technique of the present invention is simple, and operation steps is convenient, can obtain the chitin modified urethane foam of sulfur-bearing, is the enrichment of silver ions for precious metal especially.Economic worth of the present invention is higher, and efficient, the cheap function carrier material of exploitation is for concentration of precious metal, has the advantages such as simple to operate, good stability, reagent cost are low, good separating effect.Also recycled applicable to the precious metal ion in the environmental samples such as absorption trade effluent, and the separation and concentration of precious metal ion is measured.
Brief description of the drawings
Fig. 1 is the infrared spectrum of thiolated modified chitosan product;
Fig. 2 is the infrared spectrum of Chitosan-Thiolated Polymers modified rigid polyurethane foam;
Fig. 3 is that blank polyurethane foam is moulded the adsorption curve of processing different concns silver ion solution;
Fig. 4 is that the modified polyurethane foam of embodiment 1 is moulded the adsorption curve of processing different concns silver ion solution.
Embodiment
Below by specific specific examples explanation embodiments of the present invention.The present invention can also be implemented or be applied by other different embodiment, and the every details in this specification sheets also can be based on different viewpoints and application, carries out various modifications or change not deviating under spirit of the present invention.
embodiment 1
The preparation of Chitosan-Thiolated Polymers modified rigid polyurethane foam
In reaction flask, add respectively Thiovanic acid 16ml, diacetyl oxide 8ml, vibration limit, limit drip 4 vitriol oils, fully vibrate cooling after, add 2g chitosan, stir, make it under room temperature, react 1h.Then place and spend the night in dark place.Add 200mL, 2mol/LNaOH solution, puts into baking oven and dries (70 DEG C), original resolution of precipitate in solution after 12h, and now pH is 7.Add 1mg NaOH, limit edged stirs, and measuring pH value is 9 o'clock, occurs jelly shape red-purple material, and suction filtration embathes except alkali repeatedly with distilled water, makes filtrate be about neutrality.Filter cake at 50 DEG C, vacuum-drying 12h, the Chitosan-Thiolated Polymers making is placed in brown bottle and keeps in Dark Place.
Getting the Chitosan-Thiolated Polymers 1.0g making is dissolved in 100mL2wt% acetum.Get 18 10mm × 10mm × 10mm small cubes urethane foams and immerse in 50mL Chitosan-Thiolated Polymers solution, vacuumize, make to be full of in foam solution.Take out foam and be immersed in 50mL, in the glutaraldehyde solution (mol ratio that is chitosan and glutaraldehyde is 10:1) of 0.25w%, at room temperature react after 4h, repeatedly embathe and make foam be neutral with distilled water, wash away surperficial acid with distilled water, make foam surface present neutrality, be placed in baking oven dried overnight at 75 DEG C.
The modification of chitosan is mainly the reactive behavior of utilizing the multiple functional group such as hydroxyl, amino on molecular chain, by graft reaction, sugar chain, polypeptide chain, polyester chain, alkyl chain etc. is incorporated in chitosan molecule to the chitosan derivatives that forming property is different.Thiovanic acid is organic compounds containing sulfur, for making the catalyzer of epoxy resin, dihydroxyphenyl propane, is the main raw material of daily cosmetics cold hair-waving solution and trichogen.The reaction of Thiovanic acid modified chitosan is mainly carboxyl and amino reacting, certainly do not get rid of and the reacting of hydroxyl yet, because active many of the hydrogen on the specific activity hydroxyl of the hydrogen on amino, so will lack with reacting of hydroxyl.In experimentation, should obtain in theory the product of 2.6750g, and the actual product that obtains about 2.4900g, productive rate is about 93.1%.Its major cause is the loss that all can have portion of product in the operating process such as filtration, oven dry.
Fig. 1 is the FT-IR collection of illustrative plates of thiolated modified chitosan.Characteristic peak in the infrared spectra of chitosan is: 3400cm
-1the broad peak of left and right is the multi-absorption peak that the stretching vibration absorption peak of O-H and the stretching vibration absorption peak of N-H overlap to form; 2853cm
-1and 2923cm
-1methyl on chitosan ring and the C-H stretching vibration peak of methyne; 1531-1637cm
-1the acid amides I(C=O by chitosan), acid amides II(N-H) and-NH
2(1590cm
-1) wider blended absorbent bands of a spectrum forming of formation vibration peak.The infrared spectra of comparison diagram 1 thiolated modified chitosan, at 3400cm
-1the strength reduction at peak of left and right is the reaction consumption due to-NH group.At 2850-2890cm
-1there is very strong new peak-SH stretching vibration peak in place, consistent with the infrared signature frequency of the S-H stretching vibration of organic sulfide, and this explanation Chitosan-Thiolated Polymers generates.And at 1740-1750cm
-1place, particularly 1300cm
-1there is the flexible peak of stronger amides C=O in place, shows by amidate action, Thiovanic acid to be connected on chitosan.Results of elemental analyses before and after Chitosan-Thiolated Polymers modification is known, and before modification, S content is 00, and after modification, S content reaches 11.478%, and confirmation Thiovanic acid is combined with chitosan reaction.
Chitosan after thiolated modified and urethane foam are carried out to glutaraldehyde cross-linking modification, the FT-IR collection of illustrative plates that accompanying drawing 2 is modified rigid polyurethane foam.As seen from the figure, at 3138cm
-1the spectrum peak at place significantly strengthens, and this is because hydroxyl has been introduced in chitosan crosslinked modification, also has on chitosan the not amino-NH of complete reaction
2impact because glutaraldehyde is only reacted with the part amino on chitosan molecule ring in crosslinking reaction.2335.5cm
-1the peak intensity that place produces is very high, and this is because the stretching vibration of C=N group, shows on glutaraldehyde carbonyl group and urethane, chitosan-NH
2between there is Schiff alkali reaction.At 2850cm
-1there is new peak-SH stretching vibration peak in place, the intensity at peak is not very strong, consistent with the infrared signature frequency of the S-H stretching vibration of organic sulfide, and crosslinked association reaction has occurred for this explanation Chitosan-Thiolated Polymers and urethane, glutaraldehyde.
As can be seen from Table 1, in the time that the mol ratio of 1% Chitosan-Thiolated Polymers solution and glutaraldehyde consumption is 10:1, the urethane foam after institute's modification, various performance parameters significantly changes, aperture reaches 1.4mm, and water holding multiplying power reaches 31.3 times, and porosity reaches 96.4%.After modification, density polyurethane foam increases, from 30 kg/ m
3be increased to 35 kg/ m
3thereby this is because the crosslinked action of chitosan has increased the weight of polymkeric substance.Thiolated modified rear polyurethane foam aperture increases obviously, is increased to 1.4mm from 1.0mm.Before and after modification, porosity and the water holding multiplying power of urethane foam have had larger variation, are increased to 96% left and right from 80% left and right.This is mainly because chemical modification improves the total amount of the functional groups such as hydroxyl on foam, amino, sulfydryl.
The variation of urethane foam performance perameter before and after the modification of table 1 Chitosan-Thiolated Polymers
Results of elemental analyses before and after Chitosan-Thiolated Polymers modified rigid polyurethane foam is known, and unmodified urethane foam S content is 00, and after modification, S content reaches 3.625%, shows that Chitosan-Thiolated Polymers is introduced in urethane foam.Learn by electron-microscope scanning, polyurethane foam internal structure is the hole pattern being connected one by one, and these hole patterns are that foaming forms in the process of preparation polyurethane foam, in foaming process, film rupture in the middle of some hole pattern, but in the middle of many hole patterns, still there is uncracked pore membrane.Foam hole pattern structure before relatively unmodified, the film after cross-linked chitosan in polyurethane foam hole pattern structure reduces, but changes at urethane prismatic surface pattern, is because the chitosan film of surface bonding causes.
embodiment 2
The preparation of Chitosan-Thiolated Polymers modified rigid polyurethane foam
In reaction flask, add respectively Thiovanic acid 16ml, diacetyl oxide 8ml, vibration limit, limit drip 4 vitriol oils, fully vibrate cooling after, add 2g chitosan, stir, make it under room temperature, react 1h.Then place and spend the night in dark place.Add 200mL, 2mol/LNaOH solution, puts into baking oven and dries (70 DEG C), original resolution of precipitate in solution after 12h, and now pH is 7.Add 10mg NaOH, limit edged stirs, and measuring pH value is 10 o'clock, occurs jelly shape red-purple material, and suction filtration embathes except alkali repeatedly with distilled water, makes filtrate be about neutrality.Filter cake at 50 DEG C, vacuum-drying 12h, the Chitosan-Thiolated Polymers making is placed in brown bottle and keeps in Dark Place.
Getting the Chitosan-Thiolated Polymers 1.5g making is dissolved in 100mL2wt% acetum.Get 15 10mm × 10mm × 10mm small cubes urethane foams and immerse in 50mL Chitosan-Thiolated Polymers solution, vacuumize, make to be full of in foam solution.Take out foam and be immersed in 50mL, in the glutaraldehyde solution (mol ratio that is chitosan and glutaraldehyde is 10:1) of 0.25w%, at room temperature react after 4h, repeatedly embathe and make foam be neutral with distilled water, wash away surperficial acid with distilled water, make foam surface present neutrality, be placed in baking oven dried overnight at 75 DEG C.
embodiment 3
The preparation of Chitosan-Thiolated Polymers modified rigid polyurethane foam
In reaction flask, add respectively Thiovanic acid 16ml, diacetyl oxide 8ml, vibration limit, limit drip 4 vitriol oils, fully vibrate cooling after, add 2g chitosan, stir, make it under room temperature, react 1h.Then place and spend the night in dark place.Add 200mL, 2mol/LNaOH solution, puts into baking oven and dries (70 DEG C), original resolution of precipitate in solution after 12h, and now pH is 7.Add 6mg NaOH, limit edged stirs, and measuring pH value is 9 o'clock, occurs jelly shape red-purple material, and suction filtration embathes except alkali repeatedly with distilled water, makes filtrate be about neutrality.Filter cake at 50 DEG C, vacuum-drying 12h, the Chitosan-Thiolated Polymers making is placed in brown bottle and keeps in Dark Place.
Getting the Chitosan-Thiolated Polymers 2.0g making is dissolved in 100mL2wt% acetum.Get 25 10mm × 10mm × 10mm small cubes urethane foams and immerse in 50mL Chitosan-Thiolated Polymers solution, vacuumize, make to be full of in foam solution.Take out foam and be immersed in 50mL, in the glutaraldehyde solution (mol ratio that is chitosan and glutaraldehyde is 10:1) of 0.25w%, at room temperature react after 4h, repeatedly embathe and make foam be neutral with distilled water, wash away surperficial acid with distilled water, make foam surface present neutrality, be placed in baking oven dried overnight at 75 DEG C.
The quantitative contrast experiment of silver ions absorption
The preparation of silver nitrate solution: take the pure Silver Nitrate of required quality, be dissolved in the salpeter solution of 10% concentration, and in the dark constantly stir and make its dissolving.After to be dissolved, proceeded in the volumetric flask of 1L, place it at once shady place and preserve.
Measure silver ions concentration of standard solution and absorbancy curve: preparation 50mg/L silver nitrate solution, prepared silver nitrate solution is diluted to respectively to 1mg/L, 2mg/L, 3mg/L, 4mg/L, 5mg/L, 6mg/L, with atomic absorption spectrophotometry (Atomic Absorption Spectrophotometer, AAS, atomic absorption spectrophotometer best operating condition: Absorption Line wavelength 328.1nm, lamp current 2mA, air flow quantity 5L/min, acetylene gas flow 0.5L/min, burner position: 6-7mm, spectral band-width: 0.2nm) the corresponding absorbancy of mensuration respective concentration, draw the curve of silver ions concentration of standard solution and absorbancy.Gained equation is A=0.1491c-0.0383, R
2=0.9993, result is substantially linear, meets absorbancy and concentration relationship.
Modified rigid polyurethane foam is at different period Adsorption For Ag ions: preparation 50mg/L silver nitrate solution, prepared silver nitrate solution is fallen respectively to 100mL in 6 identical beakers, in each beaker, place the modified rigid polyurethane foam of the embodiment 1 to 3 of equal amts, respectively at 30min, 60min, 90min, 120min, 150min, 180min measures the variation of concentration of silver ions.Analyze above adsorption test result, modified rigid polyurethane foam reaches absorption saturation value about 3 hours.
In Comparative and Quantitative Analysis experiment, can directly measure the AgNO with the urethane foam absorption 50mg/L after modification
3solution, and can measure its saturated extent of adsorption about 3 hours.The silver ions standardized solution of configuration 50mg/L is put respectively the modified rigid polyurethane foam that 2 10mm × 10mm × 10mm small cubes are made by different proportioning Chitosan-Thiolated Polymers in three beakers that same volume (50mL) silver nitrate solution is housed.Leave standstill after 3-4 hour, measure their absorbancys separately by atomic absorption spectrophotometry, be converted into adsorptive capacity and adsorption rate is as shown in table 2.
Can find by contrast experiment: embodiment 1 reacts the modified rigid polyurethane foam obtaining, and the saturated extent of adsorption to silver ions, adsorption rate are all best.Analyze and increase with Chitosan-Thiolated Polymers acetic acid solution concentration, the reason that saturated extent of adsorption, adsorption rate decline, may be because concentration proportioning is larger, Chitosan-Thiolated Polymers acetic acid solution viscosity increases, and when cross-linking modified urethane foam, is easily filled in polyurethane foam gap, after solvent evaporates, form pore membrane and will affect mass transfer effect, while adding glutaraldehyde solution generation crosslinking reaction, reaction efficiency is declined when follow-up, affect the effect of Chitosan-Thiolated Polymers modified polyurethane.
Adsorptive capacity and the adsorption rate of the different proportioning Chitosan-Thiolated Polymers of table 2 acetic acid solution modified polyurethane to silver ions
The mechanism of analyzing thio chitosan modified polyurethane Adsorption For Ag ion, because being is cross-linked to urethane foam surface again with Thiovanic acid modified chitosan, the leading ion chelation group of introducing is-SH.Metal ion reacts with-SH's, is generally metal ion and H
+exchange: Ag
++-SH
-SAg+H
+.And the combination between them is very firm.In addition, a large amount of amino, oh group in chitosan, and the textural factor of chitosan and Thiovanic acid amidation, esterification is very beneficial for the adsorption process to precious metal ion, thereby the present invention is for adsorbing the desirable polyurethane-modified measure of precious metal.
The Chitosan-Thiolated Polymers modified rigid polyurethane foam enrichment Adsorption For Ag ion experiment of embodiment 1
The mensuration of different period Adsorption For Ag ions: preparation 50mg/L silver nitrate solution, prepared silver nitrate solution is fallen respectively to 100mL in 6 identical beakers, in each beaker, place embodiment 1 modified rigid polyurethane foam of equal amts, respectively at 30min, 60min, 90min, 120min, 150min, 180min measures the variation of concentration of silver ions.Prepare respectively again 100mg/L, 150mg/L, 200mg/L, 250mg/L silver nitrate solution, repeat above experimental procedure, measure the variation of concentration of silver ions.
Research adopts the 10g/L Chitosan-Thiolated Polymers modified rigid polyurethane foam of embodiment 1, is placed in 50mg/L, 100mg/L, 150mg/L, 200mg/L, 250mg/L different concns silver ion solution, the efficiency of enrichment Adsorption For Ag ion.Absorb enrichment, dilution metering, conversion value by time segment, show that different time sections absorbs the quality of silver ions, and for adsorbing the adsorptive capacity of different concns silver ion solution, and contrast with adopting blank urethane foam.
Fig. 3 and accompanying drawing 4 are respectively the adsorption curve of the modified rigid polyurethane foam absorption different concns silver ion solution of blank urethane foam, embodiment 1.Contrast accompanying drawing 3 and 4 can be found out: the urethane foam after the modification of embodiment 1 has better the enrichment of silver ions is absorbed than blank urethane foam, urethane foam is good carrier, can load sulfydryl, it is firmly carried in above urethane foam, and blank urethane foam also also have certain absorption inrichment to silver ions.The AgNO of blank urethane foam to different concns
3there is identical adsorptive capacity, but for the larger AgNO of concentration
3solution, rate of adsorption is more hurried up.Comparatively speaking, blank urethane foam is when absorbing the silver ions of different concns, and its adsorption efficiency is the same substantially, only has some difference above adsorption time, and blank urethane foam is shorter for silver ion solution saturated adsorption time.For the urethane foam after modification, its adsorption efficiency comparatively speaking, the higher point of its bioaccumulation efficiency of the silver ion solution of 50mg/L.
Urethane foam after modification has good separation adsorption than blank urethane foam to silver ions.Urethane foam after modification, for the AgNO of 50mg/L
3solution absorbs amount maximum.Modified polyurethane is to Ag
+adsorptive capacity (Q
t) calculate as follows:
Q
t=V（ρ
0－ρ
t）/m
In formula: Q
t---the adsorptive capacity (mg/g) of modified polyurethane; ρ
0---mass concentration in initial soln (mg/L); ρ
t---mass concentration (mg/L) in etching solution when absorption t; The volume (L) of V---solution; M---adsorbent mass.
Data measured is carried out to matching with Freundlich and Langmuir adsorption isotherm.
Freundlich isotherm formula: lgQ=(1/n) lg ρ
e+ lgK
f
In formula: Q---adsorptive capacity (mg/g); K
f, 1/n---characteristic constant; ρ
e---mass concentration when adsorption equilibrium (mg/L).
Langmuir adsorption isotherm: ρ
e/ Q=ρ
e/ Q
max+ 1/Q
maxb
In formula: Q---adsorptive capacity (mg/g); B---characteristic constant; Q
max---maximal absorptive capacity; ρ
e---mass concentration when adsorption equilibrium (mg/L).
By Ag
+isothermal adsorption test-results respectively substitution Langmuir adsorption isotherm and Freundlich isotherm formula is carried out linear regression analysis.Langmuir adsorption isotherm equation is ρ
e/ Q=0.0017 ρ
e+ 0.003, wherein Q
maxfor 104.8mg/g, b is 3.18, linear dependence degree R
2=0.9996.Freundlich isotherm formula linear dependence degree R
2=0.9546, thereby this absorption meets Langmuir isothermal adsorption more.In the time that Chitosan-Thiolated Polymers and acetic acid proportioning are 10g/L, according to Langmuir adsorption isotherm linear fit, the urethane foam after its modification is that adsorptive capacity or adsorption efficiency are all best.Its saturated extent of adsorption can reach 104.8mg/g.
After proving by experiment modification, urethane foam is to Ag
+absorption will be apparently higher than blank urethane foam to Ag
+absorption, modified rigid polyurethane foam is to Ag
+absorption meet preferably Langmuir isotherm formula, illustrate that modified rigid polyurethane foam is to Ag
+have absorption property preferably, modified rigid polyurethane foam is to Ag
+carrying out physical adsorption and chemisorption.Thiovanic acid and chitosan reaction generate Chitosan-Thiolated Polymers, then make sulfhydrylation urethane by glutaraldehyde cross-linking urethane, can be used for to precious metal ion (Ag in the environmental samples such as industrial sewage
+) enrichment or recovery.
In sum, the present invention has effectively overcome various shortcoming of the prior art and tool high industrial utilization.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Personage in affiliated technical field, not departing from the equivalence modification completing under disclosed spirit and technological thought or changing, must be contained by claim of the present invention.
Claims (5)
1. a preparation method for Chitosan-Thiolated Polymers modified rigid polyurethane foam, is characterized in that comprising the steps:
(1) in reaction flask, add respectively Thiovanic acid 16ml, diacetyl oxide 8ml, vibration limit, limit drip 4 vitriol oils, fully vibrate cooling after, add chitosan 2g, under stirring, make it under room temperature, react 1h, then in dark place place spend the night;
(2) preparation 200mL, 2mol/LNaOH solution, joins in above-mentioned reaction solution, putting into 70 DEG C of baking ovens leaves standstill after 12h, original resolution of precipitate in solution, then stirs lower adjusting and adds NaOH, measures the pH value of solution, regulate pH value, occur jelly shape red-purple material, suction filtration, embathes except alkali until filtrate is neutral repeatedly with distilled water, filter cake is vacuum-drying 12h at 50 DEG C, and the Chitosan-Thiolated Polymers making is placed in brown bottle and keeps in Dark Place;
(3) Chitosan-Thiolated Polymers making of getting 1 ~ 2g is dissolved in 100mL 2wt% acetum, gets 15 ~ 25cm
3urethane foam immerses in 50mL Chitosan-Thiolated Polymers solution, vacuumize, make to be full of in porous plastics solution, then pipette and be immersed in 50mL, in the glutaraldehyde solution of 0.25wt%, at room temperature react after 4h, repeatedly embathe and make foam be neutral with distilled water, be placed in baking oven dried overnight at 75 DEG C.
2. the preparation method of a kind of Chitosan-Thiolated Polymers modified rigid polyurethane foam according to claim 1, is characterized in that, in described step (2), under stirring, adding 1 ~ 10mgNaOH.
3. the preparation method of a kind of Chitosan-Thiolated Polymers modified rigid polyurethane foam according to claim 1, is characterized in that in described step (2), and regulating reacting liquid pH value is 9 ~ 10.
4. the preparation method of a kind of Chitosan-Thiolated Polymers modified rigid polyurethane foam according to claim 1, is characterized in that in described step (3), gets the Chitosan-Thiolated Polymers 1.0g that makes or 1.5g or 2.0g and is dissolved in 100mL 2wt% acetum.
5. the preparation method of a kind of Chitosan-Thiolated Polymers modified rigid polyurethane foam according to claim 1, is characterized in that in described step (3), gets 18 10mm × 10mm × 10mm small cubes urethane foams.
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| CN109135663A (en) * | 2018-06-12 | 2019-01-04 | 陕西科技大学 | Chitosan oligosaccharide is aoxidized for the purposes of modified polyurethane, aqueous polyurethane, adhesive and the preparation method of its preparation |
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| CN114749155B (en) * | 2022-05-10 | 2023-08-11 | 中南大学 | Sulfhydryl modified chitosan material, preparation method thereof and application thereof in adsorbing mercury ions in wastewater |
| CN116515072A (en) * | 2023-03-23 | 2023-08-01 | 广东省大湾区华南理工大学聚集诱导发光高等研究院 | Environment-friendly porous material with noble metal enrichment function, and preparation method and application thereof |
| CN116515072B (en) * | 2023-03-23 | 2023-10-20 | 广东省大湾区华南理工大学聚集诱导发光高等研究院 | Environment-friendly porous material with noble metal enrichment function, and preparation method and application thereof |
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